EP1590308B1 - Procedes de cimentation a mettre en oeuvre dans des formations souterraines utilisant de compositions de ciment renfermant des billes creuses souples - Google Patents

Procedes de cimentation a mettre en oeuvre dans des formations souterraines utilisant de compositions de ciment renfermant des billes creuses souples Download PDF

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EP1590308B1
EP1590308B1 EP04700724.0A EP04700724A EP1590308B1 EP 1590308 B1 EP1590308 B1 EP 1590308B1 EP 04700724 A EP04700724 A EP 04700724A EP 1590308 B1 EP1590308 B1 EP 1590308B1
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Prior art keywords
beads
cement
flexible
cement composition
fluid
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EP04700724.0A
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German (de)
English (en)
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EP1590308A1 (fr
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B. Raghava Reddy
Krishna M. Ravi
Michael J. Szymanski
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Halliburton Energy Services Inc
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Halliburton Energy Services Inc
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/02—Treatment
    • C04B20/04—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B16/04—Macromolecular compounds
    • C04B16/08—Macromolecular compounds porous, e.g. expanded polystyrene beads or microballoons
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B16/04—Macromolecular compounds
    • C04B16/08—Macromolecular compounds porous, e.g. expanded polystyrene beads or microballoons
    • C04B16/082—Macromolecular compounds porous, e.g. expanded polystyrene beads or microballoons other than polystyrene based, e.g. polyurethane foam
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/0016—Granular materials, e.g. microballoons
    • C04B20/002—Hollow or porous granular materials
    • C04B20/0032—Hollow or porous granular materials characterised by the gas filling pores, e.g. inert gas or air at reduced pressure
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
    • C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
    • C09K8/473—Density reducing additives, e.g. for obtaining foamed cement compositions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • This invention generally relates to cementing in subterranean formations penetrated by well bores.
  • Well cementing is a process used in penetrating subterranean zones (also known as subterranean formations) to recover subterranean resources such as gas, oil, minerals, and water.
  • a well bore is drilled while a drilling fluid is circulated through the well bore.
  • the circulation of the drilling fluid is then terminated, and a string of pipe, e.g., casing, is run in the well bore.
  • the drilling fluid in the well bore is conditioned by circulating it downwardly through the interior of the pipe and upwardly through the annulus, which is located between the exterior of the pipe and the walls of the well bore.
  • primary cementing is typically performed whereby a slurry of cement and water is placed in the annulus and permitted to set into a hard mass (i.e., sheath) to thereby attach the string of pipe to the walls of the well bore and seal the annulus.
  • a hard mass i.e., sheath
  • Low density or lightweight cement compositions are commonly used in wells that extend through weak subterranean formations to reduce the hydrostatic pressure exerted by the cement column on the weak formation.
  • Conventional lightweight cement compositions are made by adding more water to reduce the slurry density.
  • Other materials such as bentonite, diatomaceous earth, and sodium metasilicate may be added to prevent the solids in the slurry from separating when the water is added.
  • this method has the drawback that the addition of more water increases the cure time and reduces the strength of the resulting cement.
  • Lightweight cement compositions containing hollow spheres have been developed as a better alternative to the cement compositions containing large quantities of water.
  • the hollow spheres are typically cenospheres, glass hollow spheres, or ceramic hollow spheres.
  • Cenospheres are hollow spheres primarily comprising silica (SiO 2 ) and alumina (Al 2 O 3 ) and are filled with gas. Cenospheres are a naturally occurring by-product of the burning process of a coal-fired power plant. Their size may vary from about 10 to 350 ⁇ m.
  • These hollow spheres reduce the density of the cement composition such that less water is required to form the cement composition. The curing time of the cement composition is therefore reduced.
  • the resulting cement has superior mechanical properties as compared to cement formed by adding more water. For example, the tensile and compressive strengths of the cement are greater.
  • cementing compositions and applications of such compositions in subterranean formations are described in FR 2787441 , US 5779787 and GB 2354236 .
  • the cement sheath is subjected to detrimental cyclical stresses due to pressure and temperature changes resulting from operations such as pressure testing, drilling, fracturing, cementing, and remedial operations.
  • Conventional hollow spheres suffer from the drawback of being brittle and fragile and thus often cannot sustain those cyclical stresses.
  • the present disclosure relates to cement compositions that can withstand the cyclical stresses that occur during the life of the well.
  • the present invention relates to a method for cementing a well bore in a subterranean formation using cement compositions comprising hydraulic cement, water and one or more flexible beads: wherein the flexible beads are hollow, having an elastomeric, flexible outer wall and filled with a fluid, wherein in response to changes in pressure, temperature or both, the fluid expands or contracts thereby causing the elastomeric, flexible outer wall of the bead to likewise expand or contract. More specifically, the present invention relates to a method of cementing in a subterranean formation comprising the steps of:
  • a relatively lightweight cement composition is formed by combining flexible, compressible beads with a hydraulic cement and a fluid such as water.
  • Any suitable flexible, compressible bead that may expand and contract and that is compatible with a cement (i.e., chemically stable over time upon incorporation into the cement) may be combined with the cement to reduce its density.
  • Flexible bead as used herein refers to a bead that may expand and contract without adverse effect to the structure of the bead in response to changes in pressure and/or temperature.
  • Preferred flexible, compressible beads are substantially hollow objects filled with fluid (preferably gas), preferably spherical or substantially spherical in shape, and having a flexiblen outer wall.
  • Preferred flexible, compressible beads have a diameter of about 6 to 150 micrometers at 25°C and atmospheric pressure.
  • the fluid inside the flexible, compressible beads is air, carbon dioxide, an inert gas such as nitrogen, or an organic liquid with a low boiling point such as n-butane, isobutane or pentane.
  • the flexible, compressible beads have a substantially uniform, flexible outer wall comprising of one or more elastomeric materials or polymers.
  • the temperature at which the elastomeric material melts or becomes so soft that it loses its ability to contain the fluid and/or expand and contract is desirably higher than the temperature in the well bore, which may range from about 120°F (49°C) to about 400°F (204°C).
  • the elastomeric material is preferably a styrenic polymer, more preferably a copolymer of methylmethacrylate and acrylonitrile or a terpolymer of methylmethacrylate, acrylonitrile, and vinylidene dichloride.
  • Flexible, compressible beads composed of this copolymer and this terpolymer are commercially available from Akzo Nobel, Inc., which is located in Duluth, Georgia, under the tradename EXPANCEL.
  • EXPANCEL Several grades of EXPANCEL beads are available and may be selected depending upon the degree of expansion, the physical state, and the temperature range for a given application.
  • Suitable materials that may be used to form the flexible wall include, but are not limited to, a styrene-divinylbenzene copolymer and polystyrene.
  • Hollow polystyrene beads are available from many polystyrene suppliers, such as Huntsman Corporation of Houston, Texas (sold as GRADE 27, GRADE 51, or GRADE 55) and BASF Corporation of North Mount Olive, New Jersey (sold under the tradename STYROPOR).
  • the flexible, compressible beads are incorporated into the cement in a concentration of preferably from about 1% to about 200% by weight of the cement (bwoc), more preferably from about 2% to about 100%, and most preferably from about 5% to about 50%.
  • the flexible, compressible beads may be expanded before mixing with the cement by heating the flexiblen, compressible beads to soften the wall of the bead and to increase the pressure of the fluid (e.g., gas) therein.
  • Preferred flexible, compressible beads are capable of expanding up to 8 times their original diameters (i.e., the diameter at 255°C and atmospheric pressure).
  • EXPANCEL beads having a diameter in the range of 6 to 40 microns, upon expansion increase to a diameter of 20 to 150 microns. When exposed to heat, the beads can expand up to forty times or greater their original volumes. The expansion of the beads is generally measured by the decrease in the specific gravity of the expanded material.
  • the density of the beads decreases from 1,000 grams per liter for the unexpanded beads to about 30 grams per liter for the expanded beads.
  • the temperature at which the flexible, compressible beads are heated depends on the polymer composition of the bead wall and the desired density of the cement composition, which is typically in a range of from about 6 (0.72) to about 23 (2.76) lb/gal (kg/L).
  • the flexible, compressible beads may be added to the cement composition by dry blending with the cement before the addition of a fluid such as water, by mixing with the fluid to be added to the cement, or by mixing with the cement slurry consecutively with or after the addition of the fluid.
  • the beads may be presuspended in water and injected into the cement mix fluid or into the cement slurry as an aqueous slurry.
  • Surfactants may be added to the composition to water-wet the surface of the beads so that they will remain suspended in the aqueous phase even if the density of the beads is less than that of the water.
  • the surfactant are preferably nanionic, with a Hydrophile-Lipophile Balance values in the range 9-18.
  • the ability of a surfactant to emulsify two immiscible fluids, such as oil and water, is often described in terms of Hydrophile-Lipophile balance (HLB) values.
  • HLB Hydrophile-Lipophile balance
  • surfactants with higher HLB values are more hydrophilic than those with lower HLB values. As such, they are generally more soluble in water and are used in applications where water constitutes the major or external phase and a less polar organic fluid constitutes the minor or internal phase.
  • surfactants with HLB values in the range 3-6 are suitable for producing water-in-oil emulsions, whereas those with HLB values in the 8-18 range are suitable for producing oil-in-water emulsions.
  • HLB 20 ⁇ M H / M H + M L
  • M H is the formula weight of the hydrophilic portion of the molecule
  • M L is the formula weight of the lipophilic portion of the molecule.
  • ⁇ 1 is the weight fraction of surfactant # 1 in the total mixture
  • HLB 1 is the calculated HLB value of surfactant #1
  • ⁇ 2 is the weight fraction of surfactant #2 in the total surfactant mixture
  • HLB 2 is the calculated HLB value of the surfactant #2, and so on.
  • a mixture of a preferentially oil-soluble surfactant and a preferentially water-soluble surfactant provides better and more stable emulsions.
  • non-ionic ethoxylated surfactant mixtures containing from about 4 to about 14 moles of ethylene oxide.
  • the HLB ratio for a single surfactant or a surfactant mixture employed in the present invention preferably ranges from about 7 to about 20, more preferably from about 8 to about 18.
  • a cement slurry densified by using a lower water to cement ratio is lightened to a desired density by the addition of unexpanded or pre-expanded flexible, compressible beads in order to make the final cement less brittle.
  • hollow, non-flexible beads are mixed with the cement and the flexible, compressible beads.
  • Particularly suitable non-flexible beads are cenospheres, which are commercially available from, for example, PQ Corporation of Valley Forge, Philadelphia under the tradename EXTENDOSPHERES, from Halliburton Energy Services Inc. under the tradename SPHERELITE, and from Trelleborg Fillite Inc. of Atlanta, Georgia under the tradename FILLITE.
  • the non-flexible beads may be glass beads or ceramic beads.
  • the non-flexible beads, particularly the industrial waste product of the cenosphere type are relatively inexpensive as compared to the polymeric flexible, compressible beads. However, the non-flexible beads are more likely to break when subjected to downhole temperature and pressure changes and provide brittle cement compositions.
  • the flexible, compressible beads protect the ensuing hardened cement from experiencing brittle failure during the life of the well even if some of the non-flexible beads collapse. That is, the flexible wall and the gas inside of each bead contracts under pressure and expands back to its original volume when the pressure is removed, thus providing a mechanism for absorbing the imposed stress.
  • the absorption of energy by the flexible wall is expected to reduce the breakage of the more brittle beads when such compositions are used.
  • the flexible wall and the enclosed fluid also expand when the temperature in the well bore increases, and they contract when the temperature decreases. Further, the flexible, compressible beads improve the mechanical properties of the ensuing cement, such as its ductility and resilience.
  • Cement comprising flexible, compressible beads gains the following beneficial physical properties as compared to the same cement composition without the flexible, compressible beads: lower elastic (Young's) modulus, greater plastic deformation, increased tensile strength, and lower Poisson's ratio without significantly compromising other desirable properties such as compressive strength.
  • the additional costs incurred by using the flexible, compressible beads should be weighed against the benefits provided by using the flexible, compressible beads.
  • the amount of flexible, compressible beads added to the cement may be in the range of from about 2% bwoc to about 20% bwoc
  • the amount of non-flexible beads in the cement may be in the range of from about 10% bwoc to about 100% bwoc.
  • the cement utilized in the present invention is hydraulic cement, composed of calcium, aluminum, silicon, oxygen, and/or sulfur, which sets and hardens by reacting with water.
  • suitable hydraulic cements are Portland cements, pozzolana cements, gypsum cements, high alumina content cements, silica cements, and high alkalinity cements.
  • the cement is preferably a Portland cement, more preferably a class A, C, G, or H Portland cement, and most preferably a class A, G, or H Portland cement. A sufficient amount of fluid is also added to the cement to form a pumpable cementitious slurry.
  • the fluid is preferably fresh water or salt water, i.e., an unsaturated aqueous salt solution or a saturated aqueous salt solution such as brine or seawater.
  • the amount of water present may vary and is preferably selected to provide a cement slurry having a desired density.
  • the amount of water in the cement slurry is preferably in a range of from about 30% bwoc to about 120% bwoc, and more preferably in a range of from about 36% bwoc to about 54% bwoc.
  • additives may be added to the cement composition for improving or changing the properties of the ensuing hardened cement.
  • additives include, but are not limited to, set retarders such as lignosulfonates, fluid loss control additives, defoamers, dispersing agents, set accelerators, and formation conditioning agents.
  • set retarders such as lignosulfonates
  • fluid loss control additives such as lignosulfonates
  • defoamers such as lignosulfonates
  • dispersing agents such as sodium sulfonates
  • set accelerators such as sodium bicarbonate
  • formation conditioning agents such as sodium bicarbonate, sodium bicarbonate, sodium bicarbonate
  • a salt such as sodium chloride may be added to the cement composition when the drilling zone has a high salt content.
  • a well cementing process is performed using the cement composition containing the flexible, compressible beads.
  • the well cementing process includes drilling a well bore down to the subterranean zone while circulating a drilling fluid through the well bore.
  • a string of pipe, e.g., casing, is then run in the well bore.
  • the drilling fluid is conditioned by circulating it downwardly through the interior of the pipe and upwardly through the annulus, which is located between the exterior of the pipe and the walls of the well bore.
  • the cement composition comprising flexible, compressible beads is then displaced down through the pipe and up through the annulus) where it is allowed to set into a hard mass.
  • the cement composition may be used for other projects such as masonry or building construction.
  • a cement slurry containing EXPANCEL flexible, compressible beads in accordance with the present invention was formed by mixing together the following components according to the procedure described in American Petroleum Institute (APT) Specification 10, 5th Edition, July 1, 1990 : class H cement, water (117.20% bwoc); SILICALITE silica fume (16.9% bwoc); bentonite (4.0% bwoc); HALAD-344 fluid loss additive available from Halliburton Energy Services (0.5% bwoc); SCR-100 cement set retarder available from Halliburton Energy Services (0.3% bwoc); sodium chloride (18% bwoc); and defoamer (0.025 gal/sk) (0.6mL/kg).
  • API American Petroleum Institute
  • a portion of the cement slurry was then poured into 2"x2"x2" (5.1cmx5.1cmx5.1cm) brass cube molds and cured at 135°F (57.2°C) in a pressure chamber under a pressure of 5,200 psi (35.82MNm/m 2 ).
  • Another portion of the slurry was poured into 1"x2" (2.5cmx5.1cm) cylindrical steel molds and cured at the same temperature.
  • the compressive strengths were measured on 2"x2"x2" (5.1cmx5.1cmx5.1cm) molds using strength testing equipment manufactured by Tinius Olsen of Willow Grove, Pennsylvania, according to American Society for Testing and Materials (ASTM) procedure C190-97.
  • Example 1 The procedure of Example 1 was followed except that the EXPANCEL 53 beads were replaced with EXPANCEL 820 WU beads, which are composed of a terpolymer of methylmethacrylate, vinylidene bichloride, and acrylonitnie having a softening temperature above 167°F (75°C).
  • Example 1 The procedure of Example 1 was followed except that the EXPANCEL 53 beads were replaced with EXPANCEL 551 WU beads, which are composed of a terpolymer of methylmethacrylate, vinylidene dichloride, and acrylonitrile having a softening temperature above 200°F (93°C).
  • Example 1 Example 2
  • Comparative Example 1 SPHERELITE Beads, % bwoc 55 55 55 65 EXPANCEL 53 Beads, % bwoc 10 - - - EXPANCEL 820 Beads, %bwoc - 10 - - EXPANCEL 551 Beads, % bwoc - - 10 - Slurry Density, ppg @ atm.
  • the compressive strengths of the cements containing both flexible, compressible and non-flexible beads are greater than the compressive strengths of the cement containing only non-flexible beads (Comparative Example 1).
  • the Young's Modulus values of the cements in Examples 1-3 are lower than the Young's modulus value of the cement in Comparative Example 1, indicating that replacement of a portion of the brittle beads with flexible, compressible beads decreased the brittleness and improved the resiliency of the composition. Young's Modulus measures the interparticle bonding forces and thus the stiffness of a material. As such, the cements in Examples 1-3 are less stiff than the cement in Comparative Example 1, which contains no flexible, compressible beads, and at the same time remain resilient up to higher stress levels.
  • the radial strain values at yield (i.e., the elastic limit) for the cements in Examples 1-3 are much lower than the radial strain at yield for the cement in Comparative Example 1 due to the compressible nature of the flexible hollow beads under pressure.
  • the axial strain to radial strain ratios of the cements in Examples 1-3 are higher than the axial strain to radial strain ratio of the cement in Comparative Example 1. Therefore, when axial pressure is imposed on the cement column in the well bore, the radial expansion is significantly less for the cements containing both flexible, compressible and non-flexiblen beads as compared to the cement containing only non-flexible beads because of the reduction in volume of the cements containing the compressible, flexible beads.
  • a significant radial expansion under axial stress is expected for cements containing non-flexible beads such as those described in Comparative Example 1 or in cements where water is used to decrease the density.
  • the Poisson's Ratio and Young's Modulus values at yield for the cements in Examples 1-3 tend to be lower than or comparable to those values at yield for the cement in Comparative Example 1, as shown in Table 2.
  • the total area under a load vs displacement curve reflects the ability of a material to absorb the imposed stress in the direction of displacement. Comparing the areas under the radial curves for the cement compositions in Examples 1-3 and the cement compositions in Comparative Example 1 indicates the unique advantage the addition of flexible, compressible beads provides to the cement composition.
  • the beads Due to their compressible nature, the beads absorb the axial stress without having to distribute the stress in a radial direction. As a result, the radial dissipation of imposed axial stress is significantly lower for the compositions in Examples 1-3 than for the compositions in Comparative Example 1. This result clearly indicates that during the life of the well, the imposed stresses will be primarily absorbed by the flexible, compressible beads without requiting changed dimensions to the cement columns.
  • EXPANCEL 53 WU beads were suspended in three times the volume of water compared to that of the beads, and the resulting slurry was charged into a cylindrical stainless steel can provided with a lid to which a stirring paddle was connected.
  • the slurry filled 1 ⁇ 4 the available volume in the can after the lid was fitted.
  • the can was then inserted into a heated water bath of a HOWCO cement consistometer manufactured by Halliburton Energy Services.
  • the motor in the consistometer was turned which rotated the metal can while holding the lid steady.
  • the can was disassembled, and the expanded solid therein was filtered and dried in open air at ambient temperature. This procedure was repeated at different heating temperatures and times to obtain expanded beads of different specific gravities.
  • a cement slurry having a density of 11.3 pounds per gallon (1.35 kg per Litre) was prepared according to the API procedure mentioned previously by mixing class C cement with water (57% bwoc), SILICALITE fumed silica (15% bwoc), CFR-3 dispersant supplied by Halliburton Energy Services (2% bwoc), the EXPANCEL 53 WU beads of specific gravity 0.3 pre-expanded as described above (9.8% bwoc), the EXPANCEL 53 WU beads of specific gravity 0.1 pre-expanded as described above (2.6% bwoc), and a defoamer (2% bwoc).
  • the slurry was poured into cylindrical plastic containers of dimensions 2" x 4" (5.1cm x 10.2 cm), closed with lids, and cured at room temperature for 24 hours until the cement slurry solidified.
  • the plastic containers were transferred to a water bath kept at 180°F (82.2°C) for 18 hours, and the samples were submitted to cyclical load/displacement studies using the equipment described in Example 1.
  • the cyclic load/displacement studies were performed by measuring the force to break an initial sample, followed by cycling the loads of subsequent samples between 20% and 90% of the load force to break the initial sample. When the load force reached the maximum or minimum value, a two second resting time was maintained before the beginning of the next cycle.
  • the axial and radial displacements were measured as a function of load force.
  • the initial compressive strengths were measured either under no confining pressure, or a confining pressure of 1000 psi (6.89 MNm/m 2 ). The results are shown in Table 4.
  • a cement slurry having a density of 12.02 pounds per gallon (1.41 kg/L) was prepared using the API procedure mentioned in Example 1 by mixing class H cement with water (54% bwoc), unexpanded hollow polystyrene beads of EPS (expandable polystyrene) grade, ethoxylated (10 moles) nonylphenol (0.04 gallon per sack of cement), and a defoamer.
  • the slurry was poured into cubic molds as described in Example 1 and cured in an autoclave at 155°F (68.3°C) for 24 hours under a pressure of 3,000 psi (20.68 MNm/m 2 ).
  • EPS grade hollow polystyrene beads of specific gravity 1.01 were heated in water to 170°F for 3 hours following the procedure described in Example 4. The expanded beads were filtered and dried. The specific gravity of the expanded beads was 0.1.
  • a cement slurry having a 12.08 pounds per gallon (1.45 kg per Litre) density was prepared as described in Comparative Example 3 except that the unexpanded hollow polystyrene beads were replaced with the pre-expanded polystyrene beads of specific gravity of 0.1.
  • the slurry was cured under the same conditions as described in Comparative Example 3.
  • the density measured after curing under pressure was 14.9 pounds per gallon (1.79 kg per Litre), clearly indicating that pre-expansion of the beads made them flexible and compressible.

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Claims (18)

  1. Procédé de cimentation dans une formation souterraine, comprenant les étapes suivantes :
    la préparation d'une composition de ciment contenant un ciment hydraulique, de l'eau et au moins une perle flexible ; les perles flexibles étant creuses, ayant une paroi externe flexible contenant au moins un matériau élastomère et étant remplies de fluide, moyennant quoi, en réponse aux variations de pression, de température ou des deux, le fluide se dilate ou se contracte, ce qui amène la paroi externe flexible de la perle à une expansion ou à une contraction ; et
    le placement de la composition de ciment dans la formation souterraine ; et le fait de laisser la composition de ciment prendre.
  2. Procédé selon la revendication 1, dans lequel le matériau élastromère est choisi dans l'ensemble constitué d'un copolymère de méthylméthacrylate et d'acrylonitrile ; d'un terpolymère de méthacrylate de méthyle, d'acrylonitrile et de dichlorure de vinylidène ; d'un copolymère de styrènedivinylbenzène ; de résines phénoliques ; et de polystyrène.
  3. Procédé selon la revendication 1, comprenant en outre l'introduction des perles dans de l'eau avant que les perles ne soient introduites dans la composition de ciment.
  4. Procédé selon la revendication 1, comprenant en outre l'introduction d'un tensioactif ou d'un mélange de tensioactifs dans la composition de ciment, ce qui amène les perles à être en suspension dans une phase aqueuse.
  5. Procédé selon la revendication 1, comprenant en outre l'expansion des perles avant l'introduction des perles dans la composition de ciment.
  6. Procédé selon la revendication 5, dans lequel l'expansion des perles comprend le chauffage des perles.
  7. Procédé selon la revendication 1, dans lequel au moins une perle flexible est à capable d'expansion jusqu'à 8 fois son diamètre initial.
  8. Procédé selon la revendication 1, dans lequel le fluide est un liquide.
  9. Procédé selon la revendication 1, dans lequel le fluide est un gaz.
  10. Procédé selon la revendication 9, dans lequel le gaz est choisi dans l'ensemble constitué d'air, de dioxyde de carbone, d'azote, de n-butane, d'isobutène, de pentane et de leurs combinaisons.
  11. Procédé selon la revendication 1, dans lequel les perles ont un diamètre compris entre environ 6 et environ 150 µm à une température de 25 °C et sous pression atmosphérique.
  12. Procédé selon la revendication 1, dans lequel les perles sont introduites dans la composition de ciment en quantité comprise entre 1 et 200 % en poids de ciment.
  13. Procédé selon la revendication 1, dans lequel les perles sont introduites dans la composition de ciment en quantité comprise entre 2 et 100 % en poids de ciment.
  14. Procédé selon la revendication 1, dans lequel les perles sont introduites dans la composition de ciment en quantité comprise entre 5 et 50 % en poids de ciment.
  15. Procédé selon la revendication 1, dans lequel la composition de ciment comprend en outre au moins soit des perles non flexibles, soit un tensioactif, soit de la fumée de silice, soit de la bentonite, soit un agent de perte de fluide, soit un retardateur de prise, soit du chlorure de sodium, soit un agent antimousse.
  16. Procédé selon la revendication 1, dans lequel la composition de ciment comprend en outre au moins soit des sphères de céramique, soit des sphères de verre, soit des cénosphères.
  17. Procédé selon la revendication 4, dans lequel le tensioactif ou le mélange de tensioactifs a un rapport HLB compris entre environ 7 et environ 20.
  18. Procédé selon la revendication 1, dans lequel la composition de ciment a une densité comprise entre 6 et 23 livres/gal (0,72 à 2,76 kg/L).
EP04700724.0A 2003-01-24 2004-01-08 Procedes de cimentation a mettre en oeuvre dans des formations souterraines utilisant de compositions de ciment renfermant des billes creuses souples Expired - Lifetime EP1590308B1 (fr)

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Families Citing this family (99)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7482309B2 (en) * 2003-11-24 2009-01-27 Halliburton Energy Services, Inc. Methods of drilling wellbores using variable density fluids comprising coated elastic particles
US7543642B2 (en) 2003-01-24 2009-06-09 Halliburton Energy Services, Inc. Cement compositions containing flexible, compressible beads and methods of cementing in subterranean formations
US7749942B2 (en) * 2003-01-24 2010-07-06 Halliburton Energy Services, Inc Variable density fluids and methods of use in subterranean formations
GB2407317B (en) * 2003-10-20 2006-04-12 Schlumberger Holdings Cementing composition
US7376148B1 (en) * 2004-01-26 2008-05-20 Cisco Technology, Inc. Method and apparatus for improving voice quality in a packet based network
WO2005077856A1 (fr) * 2004-02-10 2005-08-25 Zachary Rich Systeme d'apport et de distribution en resine plastique pour adjuvants de beton fluides
US7607482B2 (en) 2005-09-09 2009-10-27 Halliburton Energy Services, Inc. Settable compositions comprising cement kiln dust and swellable particles
US6902002B1 (en) * 2004-03-17 2005-06-07 Halliburton Energy Services, Inc. Cement compositions comprising improved lost circulation materials and methods of use in subterranean formations
US7607483B2 (en) * 2004-04-19 2009-10-27 Halliburton Energy Services, Inc. Sealant compositions comprising colloidally stabilized latex and methods of using the same
US20050241538A1 (en) * 2004-04-28 2005-11-03 Vargo Richard F Jr Methods of making cement compositions using liquid additives containing lightweight beads
US20050241545A1 (en) * 2004-04-28 2005-11-03 Vargo Richard F Jr Methods of extending the shelf life of and revitalizing lightweight beads for use in cement compositions
US8088716B2 (en) 2004-06-17 2012-01-03 Exxonmobil Upstream Research Company Compressible objects having a predetermined internal pressure combined with a drilling fluid to form a variable density drilling mud
WO2007145735A2 (fr) 2006-06-07 2007-12-21 Exxonmobil Upstream Research Company Procédé de fabrication d'objets compressibles pour boue de forage à densité variable
US7284611B2 (en) * 2004-11-05 2007-10-23 Halliburton Energy Services, Inc. Methods and compositions for controlling lost circulation in subterranean operations
US7219732B2 (en) * 2004-12-02 2007-05-22 Halliburton Energy Services, Inc. Methods of sequentially injecting different sealant compositions into a wellbore to improve zonal isolation
US20070111901A1 (en) * 2005-11-11 2007-05-17 Reddy B R Method of servicing a wellbore with a sealant composition comprising solid latex
US20070111900A1 (en) * 2005-11-11 2007-05-17 Reddy B R Sealant compositions comprising solid latex
US7488705B2 (en) 2004-12-08 2009-02-10 Halliburton Energy Services, Inc. Oilwell sealant compositions comprising alkali swellable latex
US20070181302A1 (en) * 2004-12-30 2007-08-09 Sun Drilling Products Corporation Method for the fracture stimulation of a subterranean formation having a wellbore by using thermoset polymer nanocomposite particles as proppants, where said particles are prepared by using formulations containing reactive ingredients obtained or derived from renewable feedstocks
CA2784248C (fr) 2004-12-30 2015-02-10 Sun Drilling Products Corporation Particules nanocomposites thermodurcies, procede de production associe et utilisation dans des applications de forage de petrole et de gaz naturel
US8258083B2 (en) * 2004-12-30 2012-09-04 Sun Drilling Products Corporation Method for the fracture stimulation of a subterranean formation having a wellbore by using impact-modified thermoset polymer nanocomposite particles as proppants
US7373981B2 (en) * 2005-02-14 2008-05-20 Halliburton Energy Services, Inc. Methods of cementing with lightweight cement compositions
US7390356B2 (en) * 2005-03-11 2008-06-24 Halliburton Energy Services, Inc. Compositions for high temperature lightweight cementing
US7398827B2 (en) * 2005-03-11 2008-07-15 Halliburton Energy Services, Inc. Methods for high temperature lightweight cementing
US7264053B2 (en) * 2005-03-24 2007-09-04 Halliburton Energy Services, Inc. Methods of using wellbore servicing fluids comprising resilient material
US20060217270A1 (en) * 2005-03-24 2006-09-28 Halliburton Energy Services, Inc. Wellbore servicing fluids comprising resilient material
WO2006135892A2 (fr) * 2005-06-13 2006-12-21 Sun Drilling Products Corporation Particules thermodurcies a reticulation amelioree, leur traitement de production, et leur utilisation dans des applications de forage de petrole et de gaz naturel
US7258738B2 (en) * 2005-08-05 2007-08-21 Halliburton Energy Services, Inc. Cementing compositions including salts
US7293941B2 (en) * 2005-08-05 2007-11-13 Halliburton Energy Services, Inc. Methods for cementing using compositions containing salts
US7273949B2 (en) * 2005-08-05 2007-09-25 Halliburton Energy Services, Inc. Salts and methods for their preparation
US7607484B2 (en) 2005-09-09 2009-10-27 Halliburton Energy Services, Inc. Foamed cement compositions comprising oil-swellable particles and methods of use
US7617870B1 (en) 2008-05-14 2009-11-17 Halliburton Energy Services, Inc. Extended cement compositions comprising oil-swellable particles and associated methods
US7913757B2 (en) * 2005-09-16 2011-03-29 Halliburton Energy Services. Inc. Methods of formulating a cement composition
DK1770073T3 (da) * 2005-09-29 2009-12-14 Schlumberger Technology Bv Cementsammensætning til superkritiske carbondioxidomgivelser
DE102005046681A1 (de) * 2005-09-29 2007-04-05 Construction Research & Technology Gmbh Verwendung von polymeren Mikropartikeln in Baustoffmischungen
US7650940B2 (en) * 2005-12-29 2010-01-26 Halliburton Energy Services Inc. Cement compositions comprising particulate carboxylated elastomers and associated methods
MY163703A (en) * 2005-12-29 2017-10-13 Halliburton Energy Services Inc Cement compositions comprising particulate carboxylated elastomers and associated methods
US7645817B2 (en) * 2005-12-29 2010-01-12 Halliburton Energy Services, Inc. Cement compositions comprising particulate carboxylated elastomers and associated methods
EP2038364A2 (fr) 2006-06-07 2009-03-25 ExxonMobil Upstream Research Company Objets compressibles à garniture partielle en mousse combinés à un fluide de forage pour former une boue de forage à densité variable
EP2041235B1 (fr) 2006-06-07 2013-02-13 ExxonMobil Upstream Research Company Objets compressibles destinés à être combinés à un fluide de forage pour former une boue de forage à densité variable
US7717180B2 (en) * 2006-06-29 2010-05-18 Halliburton Energy Services, Inc. Swellable elastomers and associated methods
MX2009002959A (es) * 2006-09-20 2009-04-02 Schlumberger Technology Bv Composicion de cementacion que comprende dentro cemento sin reaccionar.
US9194207B2 (en) 2007-04-02 2015-11-24 Halliburton Energy Services, Inc. Surface wellbore operating equipment utilizing MEMS sensors
US10358914B2 (en) 2007-04-02 2019-07-23 Halliburton Energy Services, Inc. Methods and systems for detecting RFID tags in a borehole environment
US9732584B2 (en) 2007-04-02 2017-08-15 Halliburton Energy Services, Inc. Use of micro-electro-mechanical systems (MEMS) in well treatments
US9822631B2 (en) 2007-04-02 2017-11-21 Halliburton Energy Services, Inc. Monitoring downhole parameters using MEMS
US9494032B2 (en) 2007-04-02 2016-11-15 Halliburton Energy Services, Inc. Methods and apparatus for evaluating downhole conditions with RFID MEMS sensors
US9879519B2 (en) 2007-04-02 2018-01-30 Halliburton Energy Services, Inc. Methods and apparatus for evaluating downhole conditions through fluid sensing
DE102008012084A1 (de) 2007-04-02 2008-10-09 Skumtech As Brandschutz an Bauwerken
US9200500B2 (en) 2007-04-02 2015-12-01 Halliburton Energy Services, Inc. Use of sensors coated with elastomer for subterranean operations
US20080280786A1 (en) * 2007-05-07 2008-11-13 Halliburton Energy Services, Inc. Defoamer/antifoamer compositions and methods of using same
US8586512B2 (en) 2007-05-10 2013-11-19 Halliburton Energy Services, Inc. Cement compositions and methods utilizing nano-clay
US9199879B2 (en) 2007-05-10 2015-12-01 Halliburton Energy Serives, Inc. Well treatment compositions and methods utilizing nano-particles
US9206344B2 (en) 2007-05-10 2015-12-08 Halliburton Energy Services, Inc. Sealant compositions and methods utilizing nano-particles
US9512351B2 (en) 2007-05-10 2016-12-06 Halliburton Energy Services, Inc. Well treatment fluids and methods utilizing nano-particles
US8476203B2 (en) 2007-05-10 2013-07-02 Halliburton Energy Services, Inc. Cement compositions comprising sub-micron alumina and associated methods
US8685903B2 (en) 2007-05-10 2014-04-01 Halliburton Energy Services, Inc. Lost circulation compositions and associated methods
US20090038801A1 (en) * 2007-08-08 2009-02-12 Ravi Krishna M Sealant Compositions and Methods of Use
US8276666B2 (en) * 2007-08-08 2012-10-02 Halliburton Energy Services Inc. Sealant compositions and methods of use
US7878245B2 (en) * 2007-10-10 2011-02-01 Halliburton Energy Services Inc. Cement compositions comprising a high-density particulate elastomer and associated methods
US8240377B2 (en) * 2007-11-09 2012-08-14 Halliburton Energy Services Inc. Methods of integrating analysis, auto-sealing, and swellable-packer elements for a reliable annular seal
US20090176667A1 (en) * 2008-01-03 2009-07-09 Halliburton Energy Services, Inc. Expandable particulates and methods of their use in subterranean formations
US7530396B1 (en) 2008-01-24 2009-05-12 Halliburton Energy Services, Inc. Self repairing cement compositions and methods of using same
US7740066B2 (en) * 2008-01-25 2010-06-22 Halliburton Energy Services, Inc. Additives for high alumina cements and associated methods
DE102008028147A1 (de) 2008-06-14 2009-12-17 Skumtech As Wärmeisolierung im Bergbau
US7740070B2 (en) 2008-06-16 2010-06-22 Halliburton Energy Services, Inc. Wellbore servicing compositions comprising a density segregation inhibiting composite and methods of making and using same
EP2350434A2 (fr) * 2008-10-31 2011-08-03 BP Corporation North America Inc. Particules creuses élastiques pour l'atténuation de l'accumulation d'une pression annulaire
US7934554B2 (en) * 2009-02-03 2011-05-03 Halliburton Energy Services, Inc. Methods and compositions comprising a dual oil/water-swellable particle
US20100212892A1 (en) * 2009-02-26 2010-08-26 Halliburton Energy Services, Inc. Methods of formulating a cement composition
CA2703604C (fr) * 2009-05-22 2017-06-20 Lafarge Compositions cimentaires legeres
US8807216B2 (en) * 2009-06-15 2014-08-19 Halliburton Energy Services, Inc. Cement compositions comprising particulate foamed elastomers and associated methods
US9708523B2 (en) * 2009-10-27 2017-07-18 Halliburton Energy Services, Inc. Swellable spacer fluids and associated methods
WO2011066024A1 (fr) 2009-11-30 2011-06-03 Exxonmobil Upstream Research Company Systèmes et procédés pour former des objets compressibles haute performance
KR101178873B1 (ko) 2009-12-18 2012-09-03 노재호 차수 및 지반 보강용 친환경 가소성 시멘트 혼합조성물
US8691007B2 (en) 2011-09-23 2014-04-08 Georgia-Pacific Gypsum Llc Low thermal transmission building material
CN102504782B (zh) * 2011-11-21 2013-11-06 中国石油集团川庆钻探工程有限公司长庆固井公司 一种固井用轻珠防漏失水泥浆及制备工艺
US9333685B2 (en) 2012-04-19 2016-05-10 AkzoNobel Chemicals International B.V. Apparatus and system for expanding expandable polymeric microspheres
US9365453B2 (en) 2012-04-19 2016-06-14 Construction Research & Technology Gmbh Admixture and method for freeze-thaw damage resistance and scaling damage resistance of cementitious compositions
CA2884015C (fr) 2012-09-28 2019-04-23 Halliburton Energy Services, Inc. Procedes et compositions pour le traitement d'une formation souterraine a l'aide de coulis de ciment tolerant au sel
US9388685B2 (en) 2012-12-22 2016-07-12 Halliburton Energy Services, Inc. Downhole fluid tracking with distributed acoustic sensing
US20140238676A1 (en) * 2013-02-26 2014-08-28 Schlumberger Technology Corporation Cement slurry compositions and methods
US9631132B2 (en) 2013-07-11 2017-04-25 Halliburton Energy Services, Inc. Mitigating annular pressure buildup using temperature-activated polymeric particulates
US10640422B2 (en) 2013-12-06 2020-05-05 Construction Research & Technology Gmbh Method of manufacturing cementitious compositions
US9463550B2 (en) * 2014-02-19 2016-10-11 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Method of manufacturing chemical mechanical polishing layers
US9463553B2 (en) * 2014-02-19 2016-10-11 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Method of manufacturing chemical mechanical polishing layers
WO2015199678A1 (fr) 2014-06-25 2015-12-30 Halliburton Energy Services, Inc. Compositions d'obturation employant des additifs de verre gonflables
WO2016039988A1 (fr) * 2014-09-11 2016-03-17 Schlumberger Canada Limited Compositions de coulis de ciment et procédés
US20170260105A1 (en) * 2014-12-11 2017-09-14 Construction Research & Technology Gmbh Method for manufacturing a construction material
EP3230229A1 (fr) * 2014-12-11 2017-10-18 Construction Research & Technology GmbH Procédé de fabrication d'une composition cimentaire
CA2970409A1 (fr) * 2014-12-11 2016-06-16 Construction Research & Technology Gmbh Procede de fabrication de ciment
US10315955B2 (en) * 2016-06-27 2019-06-11 Tony DiMillo Annular fill compressible grout mix for use behind pre-cast concrete segment installed in time-dependent deformation tunnels
US10316239B2 (en) * 2016-06-27 2019-06-11 Tony DiMillo Compressible grout mix for use in absorbing compressive or deformation stresses of subterranean formations
CN106244124B (zh) * 2016-07-29 2018-12-25 中国石油集团渤海钻探工程有限公司 抗盐高密度早强防窜油井水泥浆
US10351750B2 (en) 2017-02-03 2019-07-16 Saudi Arabian Oil Company Drilling fluid compositions with enhanced rheology and methods of using same
CN107935440A (zh) * 2017-12-13 2018-04-20 安东石油技术（集团）有限公司 一种新型油井水泥弹塑剂及其制备方法
CN110607168B (zh) * 2019-09-28 2021-11-02 重庆威能钻井助剂有限公司 一种钻井液用降滤失剂及其制备方法
CN112012732B (zh) * 2020-10-10 2021-04-23 西南石油大学 模拟深部煤层气开采压力震荡的装置及方法
CN116847948A (zh) * 2020-12-22 2023-10-03 Cmc材料有限责任公司 具有带有聚合物型外壳的成孔剂的化学-机械抛光副垫
CN114294052B (zh) * 2022-01-04 2024-03-22 山东黄金矿业科技有限公司充填工程实验室分公司 一种改善矿山高浓度超细尾砂料浆输送性能的方法

Family Cites Families (128)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE958698C (de) * 1951-03-15 1957-02-21 Siemens Ag Verfahren zur Herstellung einer biegsamen Glasfolie fuer elektrotechnische Zwecke
DE964217C (de) * 1952-03-23 1957-05-16 Basf Ag Verfahren zur Herstellung von Bauelementen mit niedrigem spezifischem Gewicht
GB743866A (en) 1953-05-11 1956-01-25 James George Fife Improvements in or relating to hollow particles
US3044548A (en) * 1957-02-27 1962-07-17 Sinclair Oil & Gas Company Method for selectively plugging a subterranean location in a well with liquid organic resin-forming material
US3021291A (en) * 1958-12-15 1962-02-13 Koppers Co Inc Preparation of concrete containing expanded polymeric particles
US3021229A (en) * 1960-05-26 1962-02-13 Du Pont Leader film
US3214393A (en) * 1963-02-20 1965-10-26 Koppers Co Inc Concrete mixture containing expanded polystyrene and a homogenizing agent
DE1253131C2 (de) * 1963-08-17 1973-05-03 Basf Ag Verfahren zum Verbinden von organischen Kunststoffen mit mineralischen Stoffen oder anorganischen hydraulischen Bindemitteln
US3247294A (en) * 1963-11-14 1966-04-19 Bahidj B Sabouni Concrete products and methods for making same
US3306356A (en) * 1964-03-23 1967-02-28 Continental Oil Co Catalytic polymerization method
GB1118621A (en) * 1964-05-14 1968-07-03 Malcolm Jeffery Improvements in cement or plaster mixes
US3363689A (en) * 1965-03-11 1968-01-16 Halliburton Co Well cementing
DE1658436A1 (de) * 1967-07-27 1971-04-15 Basf Ag Frostschutzschicht im Unterbau von Fahrbahnen
US3766984A (en) * 1968-05-20 1973-10-23 Dow Chemical Co Method for temporarily sealing a permeable formation
US3869295A (en) * 1970-03-30 1975-03-04 Andrew D Bowles Uniform lightweight concrete and plaster
US3764357A (en) * 1970-03-30 1973-10-09 A Bowles Method of preparing lightweight concrete and plaster and the lightweight concrete and plaster thus prepared
US3649317A (en) * 1970-11-12 1972-03-14 Fuller Co Shrinkage compensating cement
US4010108A (en) * 1972-01-24 1977-03-01 Nuclear Engineering Company, Inc. Radioactive waste disposal of water containing waste using urea-formaldehyde resin
US3804958A (en) * 1972-01-27 1974-04-16 Goodmark Inc Process for making pork sausage
NL7204153A (fr) * 1972-03-28 1973-10-02
US3804058A (en) * 1972-05-01 1974-04-16 Mobil Oil Corp Process of treating a well using a lightweight cement
JPS5332369B2 (fr) 1974-03-26 1978-09-07
US4221697A (en) * 1974-05-29 1980-09-09 Imperial Chemical Industries Limited Composite materials
NL7505525A (nl) * 1975-05-12 1976-11-16 Akzo Nv Werkwijze voor de bereiding van een vorstbesten- dig beton.
US4063603A (en) * 1976-09-02 1977-12-20 Rayborn Jerry J Drilling fluid lubricant
DE2710548C2 (de) * 1977-03-10 1982-02-11 Rudolf 8019 Moosach Hinterwaldner Lagerstabile härtbare Masse und Verfahren zu deren Härtung
CH602511A5 (fr) * 1977-05-23 1978-07-31 Fresse Sa
AT359907B (de) * 1977-12-30 1980-12-10 Perlmooser Zementwerke Ag Moertel- oder betonmischung
US4306395A (en) * 1978-06-01 1981-12-22 Carpenter Orval R Lightweight cementitious product and method for making same
RO78647A (fr) * 1978-08-08 1982-03-24 Standard Oil Co,Us Procede de cimentation des puits de sonde
WO1980000426A1 (fr) 1978-08-28 1980-03-20 Leonard B Torobin Methode et appareil de production de microspheres plastiques creuses
US4304298A (en) * 1979-05-10 1981-12-08 Halliburton Company Well cementing process and gasified cements useful therein
US4340427A (en) * 1979-05-10 1982-07-20 Halliburton Company Well cementing process and gasified cements useful therein
US4234344A (en) * 1979-05-18 1980-11-18 Halliburton Company Lightweight cement and method of cementing therewith
US4303736A (en) * 1979-07-20 1981-12-01 Leonard Torobin Hollow plastic microspheres
US4303729A (en) * 1979-07-20 1981-12-01 Torobin Leonard B Hollow plastic microspheres
JPS5641859A (en) * 1979-09-07 1981-04-18 Teijin Ltd Flexible glass film
JPS5692153A (en) * 1979-12-26 1981-07-25 Japan Synthetic Rubber Co Ltd Lightweight heattinsulating mortar composition
US4302549A (en) * 1980-04-18 1981-11-24 Crowley Richard P Method of preparing expandable polystyrene
US4370166A (en) * 1980-09-04 1983-01-25 Standard Oil Company (Indiana) Low density cement slurry and its use
US4328038A (en) * 1980-11-13 1982-05-04 Bj-Hughes Inc. Resin coated aluminum
NL8201067A (nl) 1981-03-16 1982-10-18 Josef Herbert Bettendorf Bouwmateriaal en daaruit vervaardigd element.
GB2095227B (en) * 1981-03-24 1985-05-01 Cempol Sales Making lightweight concrete
US4367093A (en) * 1981-07-10 1983-01-04 Halliburton Company Well cementing process and gasified cements useful therein
US4498995A (en) * 1981-08-10 1985-02-12 Judith Gockel Lost circulation drilling fluid
US4460052A (en) * 1981-08-10 1984-07-17 Judith Gockel Prevention of lost circulation of drilling muds
US4768593A (en) * 1983-02-02 1988-09-06 Exxon Production Research Company Method for primary cementing a well using a drilling mud composition which may be converted to cement upon irradiation
US4760882A (en) * 1983-02-02 1988-08-02 Exxon Production Research Company Method for primary cementing a well with a drilling mud which may be converted to cement using chemical initiators with or without additional irradiation
US4450010A (en) * 1983-04-29 1984-05-22 Halliburton Company Well cementing process and gasified cements useful therein
US4450009A (en) * 1983-04-29 1984-05-22 Halliburton Company Method of preparing a light weight cement composition from sea water
JPS60246280A (ja) * 1984-05-18 1985-12-05 宇部興産株式会社 セメント組成物およびその製造方法
US4565578A (en) * 1985-02-26 1986-01-21 Halliburton Company Gas generation retarded aluminum powder for oil field cements
JPS62188999A (ja) 1986-02-14 1987-08-18 三井建設株式会社 廃棄物の処理方法
US4703801A (en) * 1986-05-13 1987-11-03 Halliburton Company Method of reducing fluid loss in cement compositions which may contain substantial salt concentrations
US4676317A (en) * 1986-05-13 1987-06-30 Halliburton Company Method of reducing fluid loss in cement compositions which may contain substantial salt concentrations
US4816503A (en) * 1986-06-04 1989-03-28 The Dow Chemical Company Polymer concrete having high bond strength and long working time
JP2511437B2 (ja) 1987-01-27 1996-06-26 松下電工株式会社 軽量セメント製品
US4700780A (en) * 1987-03-27 1987-10-20 Halliburton Services Method of reducing fluid loss in cement compositions which may contain substantial salt concentrations
US4806164A (en) * 1987-03-27 1989-02-21 Halliburton Company Method of reducing fluid loss in cement compositions
JPH01109551A (ja) * 1987-10-23 1989-04-26 Matsushita Electric Ind Co Ltd 光カード
JPH01157475A (ja) * 1987-12-14 1989-06-20 Alpha Home:Kk 高断熱性軽量気泡コンクリート
HUT51583A (en) 1987-12-30 1990-05-28 Karoly Kovacs Process for producing heat-insulating foam-material with inorganic binding material
US4828761A (en) * 1988-05-04 1989-05-09 The United States Of America As Represented By The United States Department Of Energy Process for impregnating a concrete or cement body with a polymeric material
US4986354A (en) * 1988-09-14 1991-01-22 Conoco Inc. Composition and placement process for oil field chemicals
HU209116B (en) 1989-10-18 1994-03-28 Kemikal Epitoeanyagipari Rt Heat-isolating powder-compositions and masses for building purposes
JPH0688823B2 (ja) * 1990-01-23 1994-11-09 ニチハ株式会社 無機質成形板およびその製造方法
US5124186A (en) * 1990-02-05 1992-06-23 Mpa Diversified Products Co. Composite tubular door beam reinforced with a reacted core localized at the mid-span of the tube
JP2918607B2 (ja) 1990-03-06 1999-07-12 花王株式会社 吸放湿性建築材料
US5320851A (en) * 1992-01-31 1994-06-14 W. R. Grace & Co.-Conn. Packaging and dispensing system for fluid and semi-fluid cement admixtures
JPH05301786A (ja) 1992-04-27 1993-11-16 Kanegafuchi Chem Ind Co Ltd 軽量コンクリート
JP3207922B2 (ja) * 1992-05-21 2001-09-10 鐘淵化学工業株式会社 軽量コンクリート
JPH06313130A (ja) 1993-04-30 1994-11-08 New Oji Paper Co Ltd 防滑性塗料組成物
US5456751A (en) * 1993-09-03 1995-10-10 Trustees Of The University Of Pennsylvania Particulate rubber included concrete compositions
JP3292578B2 (ja) 1993-12-24 2002-06-17 株式会社小松製作所 ウインチの速度制御システム
FR2714408B1 (fr) 1993-12-28 1996-02-02 Lafarge Platres Matériau à gâcher, et élément de construction obtenu avec ledit matériau.
JPH07187858A (ja) 1993-12-28 1995-07-25 Toray Ind Inc セメント系製品
US5447984A (en) * 1994-03-28 1995-09-05 Takemoto Yushi Kabushiki Kaisha Curable polymer mortar or concrete compositions
JPH07291760A (ja) 1994-04-22 1995-11-07 Kanegafuchi Chem Ind Co Ltd 充填用軽量コンクリート及びその軽量硬化物
US5458195A (en) * 1994-09-28 1995-10-17 Halliburton Company Cementitious compositions and methods
FR2729150A1 (fr) * 1995-01-06 1996-07-12 Rhone Poulenc Chimie Poudres redispersables dans l'eau de polymeres filmogenes a structure "coeur/ecorce"
US5837739A (en) * 1995-06-07 1998-11-17 Mcdonnell Douglas Corporation Loaded syntactic foam-core material
JPH09116158A (ja) * 1995-10-17 1997-05-02 Hitachi Ltd 軽量基板薄膜半導体装置および液晶表示装置
EG21132A (en) * 1995-12-15 2000-11-29 Super Graphite Co Drilling fluid loss prevention and lubrication additive
US5736594A (en) * 1996-03-28 1998-04-07 B J Services Company Cementing compositions and methods using recycled expanded polystyrene
US5839520A (en) * 1996-10-03 1998-11-24 Maillet; Bonnie Blue Method of drilling well bores
WO1998020389A1 (fr) * 1996-11-08 1998-05-14 Optical Coating Laboratory, Inc. Films de verre souple pour couverture de terminaux a ecran de visualisation
FR2762595A1 (fr) 1997-04-23 1998-10-30 Jacques Chollet Enduit ininflammable, incombustible, non fibreux
US20020039594A1 (en) * 1997-05-13 2002-04-04 Evan C. Unger Solid porous matrices and methods of making and using the same
US5900053A (en) * 1997-08-15 1999-05-04 Halliburton Energy Services, Inc. Light weight high temperature well cement compositions and methods
US5779787A (en) * 1997-08-15 1998-07-14 Halliburton Energy Services, Inc. Well cement compositions containing rubber particles and methods of cementing subterranean zones
JPH11268962A (ja) 1998-03-20 1999-10-05 Harima Ceramic Co Ltd 断熱性キャスタブル耐火物
US6328038B1 (en) * 1998-07-14 2001-12-11 Fred Bruce Kessler Nasal cannula retainer
JP2953576B1 (ja) * 1998-09-18 1999-09-27 鹿島建設株式会社 コンクリート表面のひび割れ防止法
US6279652B1 (en) * 1998-09-23 2001-08-28 Halliburton Energy Services, Inc. Heat insulation compositions and methods
FR2784095B1 (fr) * 1998-10-06 2001-09-21 Dowell Schlumberger Services Compositions de cimentation et application de ces compositions pour la cimentation des puits petroliers ou analogues
EA002938B1 (ru) * 1998-11-13 2002-10-31 Софитек Н.В. Цементирующая композиция и ее применение для цементирования нефтяных скважин или подобных сооружений
FR2787441B1 (fr) 1998-12-21 2001-01-12 Dowell Schlumberger Services Compositions de cimentation et application de ces compositions pour la cimentation des puits petroliers ou analogues
US6197418B1 (en) * 1998-12-21 2001-03-06 Agfa-Gevaert, N.V. Electroconductive glass laminate
RU2154619C1 (ru) * 1999-01-05 2000-08-20 Котляр Владимир Дмитриевич Легкий бетон
ES2380414T3 (es) * 1999-01-29 2012-05-11 Sika Technology Ag Procedimiento para la reducción de la contracción de agentes aglutinantes hidráulicos
DE10033815A1 (de) 1999-07-12 2001-01-18 Lothar Mansfeld Zementgebundener Sielbaustoff
FR2796935B1 (fr) * 1999-07-29 2001-09-21 Dowell Schlumberger Services Coulis de cimentation des puits petroliers ou analogues a basse densite et basse porosite
CA2318703A1 (fr) 1999-09-16 2001-03-16 Bj Services Company Compositions et methodes de cimentation utilisant des particules elastiques
FR2799458B1 (fr) * 1999-10-07 2001-12-21 Dowell Schlumberger Services Compositions de cimentation et application de ces compositions pour la cimentation des puits petroliers ou analogues
AU2001231075A1 (en) * 2000-01-24 2001-07-31 Robert R. Wood Improved drilling fluids
US6444316B1 (en) * 2000-05-05 2002-09-03 Halliburton Energy Services, Inc. Encapsulated chemicals for use in controlled time release applications and methods
US6530437B2 (en) * 2000-06-08 2003-03-11 Maurer Technology Incorporated Multi-gradient drilling method and system
GB2365859B (en) * 2000-08-18 2002-09-04 Earth Link Technology Entpr Lt Cementitious construction materials containing rubber
US6457524B1 (en) * 2000-09-15 2002-10-01 Halliburton Energy Services, Inc. Well cementing compositions and methods
GB0024688D0 (en) * 2000-10-09 2000-11-22 Dyno Specialty Polymers As Process
US6739408B2 (en) 2000-10-30 2004-05-25 Baker Hughes Incorporated Apparatus and method for preparing variable density drilling muds
US6545066B1 (en) * 2000-11-28 2003-04-08 United States Gypsum Company Lightweight ready-mix joint compound
US6536540B2 (en) 2001-02-15 2003-03-25 De Boer Luc Method and apparatus for varying the density of drilling fluids in deep water oil drilling applications
RU2178320C1 (ru) * 2001-04-02 2002-01-20 Винниченко Юрий Алексеевич Способ фотополимеризации светоотверждаемых пломбировочных адгезивных материалов
US6367549B1 (en) * 2001-09-21 2002-04-09 Halliburton Energy Services, Inc. Methods and ultra-low density sealing compositions for sealing pipe in well bores
US6644405B2 (en) 2002-03-21 2003-11-11 Halliburton Energy Services, Inc. Storable water-microsphere suspensions for use in well cements and methods
US6732800B2 (en) * 2002-06-12 2004-05-11 Schlumberger Technology Corporation Method of completing a well in an unconsolidated formation
US6641658B1 (en) * 2002-07-03 2003-11-04 United States Gypsum Company Rapid setting cementitious composition
US6516883B1 (en) * 2002-07-25 2003-02-11 Halliburton Energy Services, Inc. Methods of cementing pipe in well bores and low density cement compositions therefor
US6757919B2 (en) * 2002-08-27 2004-07-06 Sloan Valve Company Automatically operated handle-type flush valve
US7494544B2 (en) * 2003-01-23 2009-02-24 Bj Services Company Polymer shell encapsulated gas as a cement expansion additive
US7543642B2 (en) 2003-01-24 2009-06-09 Halliburton Energy Services, Inc. Cement compositions containing flexible, compressible beads and methods of cementing in subterranean formations
US7482309B2 (en) * 2003-11-24 2009-01-27 Halliburton Energy Services, Inc. Methods of drilling wellbores using variable density fluids comprising coated elastic particles
US6962201B2 (en) * 2003-02-25 2005-11-08 Halliburton Energy Services, Inc. Cement compositions with improved mechanical properties and methods of cementing in subterranean formations
US7147055B2 (en) * 2003-04-24 2006-12-12 Halliburton Energy Services, Inc. Cement compositions with improved corrosion resistance and methods of cementing in subterranean formations
US6904971B2 (en) * 2003-04-24 2005-06-14 Halliburton Energy Services, Inc. Cement compositions with improved corrosion resistance and methods of cementing in subterranean formations
US20040244978A1 (en) * 2003-06-04 2004-12-09 Sun Drilling Products Corporation Lost circulation material blend offering high fluid loss with minimum solids
US6902001B2 (en) * 2003-06-10 2005-06-07 Schlumberger Technology Corporation Cementing compositions and application of such compositions for cementing oil wells or the like

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US20050061206A1 (en) 2005-03-24
EP3012238A1 (fr) 2016-04-27
CA2513561C (fr) 2012-03-27
WO2004065321A1 (fr) 2004-08-05
US20040144537A1 (en) 2004-07-29
US7543642B2 (en) 2009-06-09
AR042918A1 (es) 2005-07-06
CA2513561A1 (fr) 2004-08-05
EP3012238B1 (fr) 2018-12-05
NO344261B1 (no) 2019-10-21
NO20053778L (no) 2005-08-23
EP1590308A1 (fr) 2005-11-02

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